Doubly Charged Four-Membered Ring Systems: Cyclobutadiene Dianions and Heavy Cyclobutadiene Dianions

Akira Sekiguchi; Tsukasa Matsuo

doi:10.1055/s-2006-950280

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Synlett 2006(17): 2683-2698
DOI: 10.1055/s-2006-950280

ACCOUNT

Doubly Charged Four-Membered Ring Systems: Cyclobutadiene Dianions and Heavy Cyclobutadiene Dianions

Akira Sekiguchi*^a, Tsukasa Matsuo^b
^a Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Fax: +81(298)534314; e-Mail: sekiguch@staff.chem.tsukuba.ac.jp;
^b Coordination Chemistry Laboratories, Institute for Molecular Science, Okazaki, Aichi, 444-8787, Japan
Fax: +81(564)595589; e-Mail: tmatsu@ims.ac.jp;

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Publikationsverlauf

Received 13 February 2006
Publikationsdatum:
09. Oktober 2006 (online)

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Abstract

Recent progress in the experimental chemistry of cyclobutadiene dianions (CBD^2-s) containing a doubly charged four-membered ring system is reviewed. New families of silyl-substituted CBD^2-s, cyclobutadienes (CBDs), and tetrahedranes are covered in detail. The aromaticity of the tetrasilyl- and diphenyldisilyl-CBD^2-s have been studied on the basis of structural characteristics and magnetic properties. All of the CBD^2-s show a strong diatropic ring current resulting from six π-electron system. The preparation of CBD^2- derivatives consisting of heavier group 14 elements (Si and Ge) is also included. They demonstrate a non-aromatic nature with a folded four-membered ring.

1 Introduction
2 Cyclobutadiene Dianions (CBD^2-s)
2.1 Preparation of CBD Complexes
2.2 Transmetalation of CBD Complexes
2.3 Tetrasilyl-CBD^2-s
2.4 Diphenyl-Disilyl-CBD^2-s
3 Cyclobutadienes (CBDs)
4 Tetrahedranes
5 Heavy Cyclobutadiene Dianions (CBD^2-s)
6 Conclusion

Key words

silicon - small-ring systems - cyclobutadiene dianions - cyclobutadienes - tetrahedranes - aromaticity - cage compounds - germanium

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3

A thematic issue of aromaticity, edited by von Ragué Schleyer, P., has been published: Chem. Rev. 2001, 101, 1115-1566.

36

Tanaka, M.; Sekiguchi, A. unpublished results.